Alkoxy-naphthalenes



United States atent O 3,031,464 ALKOXY-NAPHTHALENES V Hyman M. Molotsky,Chicago, Ill., assignor to Velsicol Chemical Corporation, Chicago, 111.,a corporation of Illinois No Drawing. Filed Nov. 28, 1958. Ser. No.776,729

6 Claims. (Cl. 260-6462) This invention relates to new halogenatedcompositions of matter. In particular, this invention relates to new,unique halogenated ethers possessing advantageous insecticidal activityand which are also extremely useful as intermediate chemicals. Thisapplication is a continuation-in-part of my copending application SerialNo. 651,173, filed April 8, 1957, now abandoned.

The presence of an ether group results in novel compositions whichpossess unexpectedly high toxicity to certain specific organisms and inaddition have other highly desirable properties, particularly thoserelating to solubility. These enhanced characteristics promoted by thepresence of the ether group will also be retained in compounds preparedfrom this valuable composition by epoxidation, halogenation, and otherreactions which do not impair the configuration of said compositions.

While the new ethers are most desirable compositions, their preparationdid not appear to be feasible in a direct process on the basis of thework of Krynitsky and Best, 69 J.A.C.S. 1918. This reaction of Krynitskyet a1. produced a ketal and not the ether which would be operable in thepresent invention to prepare the desired compositions. Thus, theliterature discloses the extreme dif ficulty in preparing the newcompositions of this invention.

It is therefore an object of the present invention to produce newhalogenated ethers.

Another object of the present invention is the preparation of newinsecticidally active compositions of matter.

Still another object of the present invention is the preparation of anew organic composition of matter from which other valuable compositionsof matter may be prepared.

Other objects of the present invention will become apparent from theensuing description.

Unexpectedly, it has been found that the new compositions of matter maybe prepared by reacting hexachlorobicyclo-(2.2.l)-heptadiene with anorganic alcohol in the presence of an alkaline reacting material such aspotassium or sodium hydroxide, and adducting this product with aconjugated diene, particularly cyclopentadiene, methyl cyclopentadiene,butadiene, and furan, in a Diels-Alder manner.

From the literature it would be expected that this reaction ofhexachlorobicyclo-(2.2.1)-heptadiene with an organic alcohol wouldresult in either a ketal by means of the replacement of both bridgechlorine atoms or in no reaction. It is certainly unusual and unexpectedthat only one said chlorine atom should be replaced, resulting in thepreparation of the desired ethers.

The scope of this novel reaction is not limited by the size or structureof the organic alcohol. Thus, aliphatic hydrocarbon alcohols containingup to 14 carbon atoms are operable herein.

The starting material, hexachlorobicyclo-(2.2.l)-heptadiene can beprepared in known manner, such as by the dehydrohalogenation of theequimolar Diels-Alder adduct of hexachlorocyclopentadiene and vinylchloride, and is not critical to the present invention.

The following examples illustrate the preparation of the newcompositions of the present invention but should not be construed asimposing limitations on the scope of the present invention.

"ice

EXAMPLE I Preparation of 1,2,3,4,7-PentachZoro-7-Isopr0p0xybicyclo-(2.2.1 -2,5-Heptadiene water, dried over anhydrous sodium sulfate andthe diethyl ether removed by distillation under reduced pressure. Thedesired product was recovered by fractionation of the residue of thediethyl ether removal as the fraction with a boiling point of 99-105 C.at 0.8 mm. of

Hg pressure. This crude product was purified by chro matographic means.Its boiling point was found to be 105 C. at 0.8 mm. Hg and itsrefractive index N 1.52.13.

The compound was analyzed for C H Cl O:

G i H Cl Theoretical 37. 24 2. 81 54. 97 Found 36. 89 2. 85 55. 43

1 Its structure is:

EXAMPLE ll Equimolar Adduction of 1,2,3,4,7-Pentachl0ro-7-Isopropoxybicyclo (2.2.1)-2,5-Heptaziiene and Cyclopentadiene 1,2,3,4,7-pentachloro-7-isopropoxybicyclo (2.2.1 -2,5- heptadiene (94.5grams; 0.29 mol) was placed in a threenecked glass reaction vesselequipped with stirrer, thermometer, heating mantle and addition funneland heated to C. Cyclopentadiene (31.9 grams; 0.49 mol) was added fromthe addition funnel into the reaction vessel uniformly over a period of1 /2 hours. The reaction mixture was maintained at 130 C. for anadditional 3 hours after the completion of the cyclopentadiene addition.The desired product was obtained by fractionation of the reactionmixture as the fraction boiling at l30131 C. at 0.2 mm. Hg pressure andhaving a refractive index of 1.5554 (at 20 C.). The product,1,2,3,4,10-pentachloro 10-isopropoxy-1,4,4a,5,8,8a-hexahydro-1,4,5,8dimethanonaphthalene, solidified on standing and was foundto have a melting point of 71-73 C.

The product was analyzed for C H CI O:

3 EXAMPLE m Preparation of 1,2,3,4,7-Pentachlaro-7-Eth0xybicyclo(2.2.1)-2,5-Heptadiene 1,2,3,4,7,7 hexachlorobicyclo (2.2.1)2,5-heptadiene (600 grams; 2.0 mol) was placedin a three-necked glassreaction vessel equipped with stirrer, thermometer, heating mantle andrefiux condenser and containing potassium hydroxide (204 grams; 3.6 mol)and ethyl alcohol (670 grams; 14.6 mol). Thereaction mixture was heatedto reflux. and allowed to reflux for 5 hours.

At the end of the five-hour reaction time, the unreacted alcoholwasremoved by use of reduced pressure. The residue from thisdistillation was immersed in water and extracted with diethyl ether.This ether layer was separated from the aqueous, layer and dried overanhydrous sodium sulfate. The desired product was then recoveredbydistillation as. the fraction boiling at 118 C. at 1.5 mm. Hg.pressure. It was found to-have a refractive index at 20 C. of 1.5330. Itwas analyzed for chlorine content of C H Cl O:

Theoretical 57.48 Found 57.50

Its structure is:

Gl- =OG EF EXAMPLE IV Equimolar Adduction of1,2,3,4,FPgntachloroJ-Ethoxy- Bicyclo (2.2.1)-2,5-Heptadiene and FuranEXAMPLE V Equimolar Adduction, of 1,2,3,4,7-Pentaclilro-7-Eth0xy Bicyclo(2.2.1 )-2,5-Heptadiene and Cyclopentadienel,2,3,4,7-pentachloro-7-ethoxy' bicyclo (2.2.1)-2,5-hept-adiene (60grams; 0.19, mol) was placed in a three necked glass reaction vesselequipped with stirrer, the mometer, addition funnel and heatingmantleand heated to about 100 C. Cyclopentadiene (28.4 grams; 0.43 mol) wasadded dropwise from the addition funnel into the reactionvessel'uniforrnly over, a period of 1 /2 hours. The reaction mixture wasmaintained at approximately 100 C. for an additional 1% hours, at whichtime the reaction mixture was distilled under reduced pressure with thedesired adduct being recovered as the fraction boiling at 140 C. under0.3 mm. Hg pressure. This product, 1,2,3,4,10pentaohloro-10-ethoxy-l,4,4a,5,8,8a-

hexahy-dro-1,4,5,8-dimethanonaphthalene, solidified and was found tohave a melting point of 104.5106 C. It was analyzed for C H Cl O:

Theoretical 44.89 47.34 3.50 Found 45.03 47.40 3.70

EXAMPLE.VI

Equimolar Adduction of 1,2,3,4,7-Pentachl0r0-7-Ethoxy Bicyclo(2.2.1)-2,5-Heptadiene and Methyl Cyclopentadiene EXAMPLE VIIPreparation 0 1,2,3,4,7-Pentnchl0ro-7-Meth0xyl Bicyclo2.Z.1)-2,5-Heptadz'erze l,2,3,4,7,7 hexachlorobicyclo(2.2.1)-2,5-heptadiene (604 gran1s;'2.02 mol) isplaced in a three-neckedglass reaction vessel equipped with stirrer, heating mantle, thermometerand reflux condenser and containing potassiurn hydroxide (190 grams;2.90 mol) and methyl alcohol (480 grams; 15.0 mol). The reaction mixtureis heated toreflux and maintained at reflux for approximately 4 hours.The unreacted material is removed by distillation under reducedpressure. The desired product is recovered by extracting the residuewith diethyl ether, washing this extract with water, drying it overanhydrous sodium sulfate and a final distillation.

EXAMPLE VIII Equimolar Adauction of 1,2,3,4,7-Pentachloro-7-Meth0xyBicycle (2;2..1)-2,5-Heptadiene and Butadienel,2,3,4,7-pentachloro-7-methoxy bicyclo (2.2.1)-2,5- heptadiene (141.5grams; 0.5 mol) is placed in a threenecked glass reaction vesselequipped with stirrer, heating mantle, thermometer and addition funneland heated to about C. added dropwise from the addition funnel into thereaction vessel uniformly over a period of 1 /2 hours. The reactionmixture is maintained at about 100 C. for an additional 1 /2 hours atwhich. time the desired equimolar adduct,1,2,3,4,10-'pentachloro-10-methoxy-1,4,4a,5,8,8ahexahydror1.,4-methanonaphthaleneis recovered from the reaction mixture by distillation.

The above examples illustrate the preparation of the new compositions ofmatter of the present invention, but of course do not describe everyspecie contemplated by this invention whichmay be described as acomposition obtained by the reaction consisting of the equimolaradduction of a conjugated diene, particularly cyclopentadiene, methylcyclopentadiene, butadiene and furan, andthe composition having thefollowing structure:

wherein R is an alkyl radical containing up to 14 carbon atoms.

This reaction is more commonly referred to as a Diels- Alder adductionwith the composition of the above structure acting as the dienophile. Aspreviously indicated,

1,3-butadiene (59.4 grams; 1.1 mol) is the dienophile of the presentprocess is prepared by the reaction of 1,2,3,4,7,7 hexachlorobicyclo(2.2.1)-2,5- heptadiene and the desired alcohol in the presence of analkaline reacting material.

The following list describes the alcohols applicable in the presentinvention and the product of their reaction with1,2,3,4,7,7-hexachlorobicyclo (2.2.l)-2,5-heptadiene in the presence ofan alkaline reacting material. It is to be understood that the variousisomers of these alcohols are equally applicable.

Alcohol Product (1) methyl 1, 2, 3 4,7-pentachloro-7-methoxy-bicyelo-(2.2.1)- 2,5-l1eptad1ene. (2) ethyl 1,2, 3,4, 7 pentach10ro-7-ethoxy-b1eyclo-(2.2.1)-

2,5-heptad1ene. (3) butyl 1, g, 1?,d-pentachloro-7-butoxy-bicyclo-(2.2.1)-2,

ep a lene. (4) propyl 1, 22, 3,4,t'igentachloro-7-propoxy-bicyelo-(2.2.1)-

ep a lane. (-5) pentyl 1, 2, 8, 4, 7-pntachloro-7-pentoxy-bicyclo-(2.2.1)-

2,5-heptad1ene. (6) hexyl 1, 52,113,g-pentaehloro-7-hexoxy-b1cye1o-(2.2.1)-2,

ep a lene. (7) heptyl 1, 2, 3, 4, 7-pentachloro-7-heptoxy-biweb-(2.2.1)-

2,5-heptad1ene. (8) oetyl 1, 52,113, ,(3pentaehlro-7-octoxy-b1cye1o-(2.2.1)-2,

e a lene. (9) nonyl 1, 2, 3, 4,7-pentachloro-7-nonoxy-bicyclo-(2.2.1)-2,

fi-heptadiene. (10) deeyl 1, 52,113, at,'-pentachl0ro-7-dec0xy-b1cyc1o'(2.2.1)-2,

ep :1 1ene (11) undecyl 1, 3, 3 'l -pdentaehloro-7-undecoxy-bicyclo-(2.2.1)-

ep a ene. (12) dodecyl 1, 22,53h4,'lfi-pentachloroJ-dodecoxy-bicyclo-(2.2.1)-

ep a lene. (13) tridecyl 1, 2153114,7t-p(fntach1oro-7-tridecoxy-bicyclo-(2.2.1)-

2 ep a ienep (14) tetradeeyl 1, '2, 3, 4, 7-pentaehloro-7-tetradecoxybicyclo- (2.2.1)-2,5-heptadiene.

This reaction can be performed in the presence or absence of solvent;under atmospheric pressure, superatmospheric pressure, or subatmosphericpressure; as a continuous process or a batch process; and with otherlike innovations. v H

In accordance with the present invention, the previously describedethers are reacted with a diene, particularly a diene selected from thegroup consisting of cyclopentadiene, methyl cyclopentadiene, furan andbutadiene, in a Diels-Alder manner. This Diels-Alder adduction can beperformed in the absence or presence of solvent, although it ispreferred not to use solvent in order to simplify the recoveryprocedure. Temperatures between about 100 C. to about 200 C. aresatisfactory, although lower or higher temperatures can be used. Thisreaction can 0 be performed at pressures below or above atmosphericpressure and as a batch or continuous process, the latter beingdesirable from an economic viewpoint.

Thus the compounds of the present invention can be said to berepresented by the group consisting of the following structuralformulas:

and

III

of II; and when butadiene (d) is utilized as the diene, the

product has the structural formula of III.

Exemplary of the compounds of the present invention and theirpreparation are the following wherein the reactants are numbered andlettered as hereinbefore indicated:

1,2,3 ,4,lO-pentachloro-lC-methoxy 1,4,4a,5,8,

8ah'exahydro 1,4,5 ,8 dimethanonaphthalene 1,2,3,4,10-pentachloro-l0butoXy 1,4,4a,5,8, 8ahexahydro 1,4,5,8 dimethanonaphthalene 1,2,3,4,10-pentachloro-10-heptoxy 1,4,4a,5 ,8,

8a-hexahydro 1,4,5 ,8 dimethanonaphthalene 1,2,3,4,l0-pentachloro-l0nonoxy l,4,4a,5, 8,

8ahexahydro 1,4,5,8 dimethanonaphthalene1,2,3,4,10rpentachloro-IO-tridecoXy-l,4,4a,5,8, 8ahexahydro 1,4,5,8dimethanonaphthalene l,2,3,4,l0-pentachloro-9- methoxy 1,4,4a,5 ,8,Sa-hexahydro-1,4-methano-5,8-oXa-naphthalene 1,2,3,4,10-pentachloro-9propoxy 1,4,4a,5 ,8, 8a-hexahydro-1,4-methano-5,S-QXa-naphthalene1,2,3,4,9-pentachloro-9-pentoxy 1,4,4a,5,8,8ahexahydro-lA-methano- 5,8oXa naphthalene l,2,3,4,9-pentachloro-9 isooctoxy l,4,4a,5,8,8a-hexahydro-1,4-methano-5,8-oxa-naphthalene l,2,3,4,9-pentachloro-9-decoxy 1,4,4a,5,8,8ahexahydro-1,4-methano-5 ,8 oXa naphthalene Vl,2,3,4,9-pentachloro-9-tetradecoxy-1,4,4a,5,8,Sa-hexahydro-1,4-rnetl1ano-5,8-oxa-naphthalene 1,2,3,4,9-pentachloro9-ethoXy 1,4,4a,5,8,8a-

heXahydro-l,4-methanonaphthalene l,2,3,4,9-pentachloro 9 isopropoxy1,4,4a,

5,8,8a hexahydro 1,4 methanonaphthalene 1,2,3,4,9-pentacl1loro-9-hexoxy1,4,4a,5,8,8a-

hexahydro-l,4-methanonaphthalene 1,2,3,4,9-pentachloro-9- octoXyl,4,4a,5,8,8a-

heXahydro-l,4-methanonaphthalene 1,2,3,4,9-pentach1oro- 9dodecoxy-1,4,4a,5,8, Sa-hexahydro-1,4-methanonaphthalene 1,2,3,4,9pentachloro 9 tetradecoxy 1,4,

4a,5,8,8a-hexahydro 1,4 methanonaphalene (14)+(d)1,2,3,4,lO-pentachloro-lO-methoxyl,4,4a,5,8,

Sa-hexahydro--methyl-1,4,5 ,8 dimethano-1,2,3,4,lO-pentachloro-lO-undecoxy 1,4,4a,5,8,Sa-hexahydro--methyl-l,4,5,8dimethanonaphthalene (11) (b) 1,2,3 ,4, lO-pentachlorolO-tetradecoxy 1,4,4a,

5,8,8a-heXahydro-6-methyl-1,4,5,8 dimethanonaphthalene (-l 4) (b) Aspreviously described, all of the present compounds can be prepared bythe adduction of the appropriate hexachlorobicycloheptadiene ether and adiene selected from the group consisting of cyclopentadiene, methylcyclopentadiene, butadiene and furan in a Diels-Aldcr manner. The ethergroup of the dienophile will not be afiected by this reaction and thuswill be a constituent of the final product.

As previously indicated, the compositions of the present invention havesuperior insecticidal activity. This desirable propensity is verified bythe following data which shows the high toxicity of the compositions ofthe present invention to various undesirable organisms. In all of thefollowing tests the compound tested was the product ofthe equimolaradduction of 1,2,3,4,7-pentachloro- 7-isopropoxybicyclo(,2.2.1)-2,5-heptadiene and cyclopentadiene.

In all of these tests the test compound was formulated into a 10%wettable powder, dispersed in water at the indicated concentration ofactual chemical and applied bydipping the cranberry bean host plantstherein. After the treated plants had dried, untreated insects werecaged thereon.

- Percent Percent Mortality Organism Actual 48Hours Compound AfterTreatment Mexican Bean Beetle 0. 2 100 SouthernArmyWorm 0. 4 100 Do 0.2100 0. l 100 0.05 100 0.025 80 These compositions may be usedin theirpure former a ingredients with the desired carrier by means known to theart of formulation. Carriers which may be used include diatomaceousearth, fullers earth, bentonite, lime products, and the like.

When a solid carrier is employed, it is desirable that the formulationbe in a finely divided form. This may beobtained by grinding. It isoften advantageous to add small amounts of wettingagents to-theformulation. For

spray application the. activeingredient may be dissolved,

or dispersedi'rr a suitable liquid carrier. Spraycompositionscontaining. the active ingredient in the form of a solution,suspension, dispersion or emulsionrnay be employed.

The following formulations maybe used:

FORMULATION. .4;

Percent by weight Product of Example 11 2s Celite 209 75 Celite 209 is adiatomaceous earth.

FORMULATION B Percent by weight Product of Example IV 50 Micro Cel A 47Triton X- 3 Product of Example V 60 Isopropyl acetate 23 Isopropylalcohol 10 Atlas G-1690 7 Atlas 6-1690 is a commercially obtainableemulsifier. This formulation is an emulsifiable concentrate.

Inaddition to its above demonstrated insecticidal activity, thecompositions of the present invention are also valuable as chemicalintermediates. There can be prepared from it several highly usefulcompounds. These compounds are prepared by reaction of theunsaturatedcarbon to carbon bond located in the portionof'the molecule not a partof its bicyclo-heptane moiety.

Thus, the compositions of the present invention may be oxidized,halogenated, and other reactions performed with this unsaturated linkageas are performable with other olefinic bonds. However, the products whenusing the present compositions of matter contain the valuablepentachlorobicycloheptene ether configuration.

I claim as my invention:

1. A new composition of matter selected from the group consisting of:

wherein R is an alkyl radical containing up to 14 carbon atoms and A- isselected from the group consisting of hydrogen and methyl.

2. 1,2,3,4,l0 pentachloro 10 ethoxy1,4,4a,5,8,8ahexahydro-l,4,5,8-dimethanonaphthalene.

3. 1,2,3,4,10 pentachloro l0 isopropoxy l,4,4a,5,8,8a-hexahydro-1,4,5,S-dimethanonaphthalene.

1 10 4. 1,2,3,4,9 pentachloro 9 ethoxy 1,4,4a,5,8,8a- 2,655,513 KleimanOct. 13, 1953 hexahydro-l,4-methano-5,8-oxa-naphthalene. 2,655,514Kleiman Oct. 13, 1953 5. 1,2,3,4,9 pentachloro 9 methoxy 1,4,4a,5,8,8a-2,697,103 Ordas Dec. 13, 1954 hexahydro-1,4-methanonaphthalene.

6. 1,2, 3,4,9 pentachloro 9 ethoxy 1,4,4a,5,8,8a- 5 OTHER REFERENCEShexahydm'6'methyl'1r453'dunethanonaphthalene- Frear et al.: Journal ofEconomic Entymology, vol. 40

(1947, pages 736-41). References Cited m the file of thlws patentPatterson et al.: The Ring Index (second edition, 1960),

UNITED STATES PATENTS pages 329 and 540 2,635,979 Lidov Apr. 21, 1953 1UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,031,464 April 24, 1962 Hyman M. Molotsky corrected below.

Column 6, lines 44 and 47, for "l,2,3,4,lO-", each occurrence, read 12,3,

(SEAL) Attest:

ERNEST w. SWIDER DAVID LADD Attesting Officer Commissioner of Patents

1. A NEW COMPOSITION OF MATTER SELECTED FROM THE GROUP CONSISTING OF: